Sustainable Network Polymers Enabled by Radical-Mediated Dynamic Covalent Chemistry

Abstract

Network polymers have long been regarded as materials with limited sustainability compared to linear polymers with excellent processability and recyclability. This comprehensive review outlines the design and functional development of sustainable network polymers incorporating bulky disulfide linkages as cross-linking points, based on radical-mediated dynamic covalent chemistry. This molecular motif can reversibly generate radicals under mild thermal conditions. The authors designed and synthesized derivatives bearing this molecular motif, quantitatively evaluated their exchange behavior, and successfully introduced them into polymer networks. As a result, a series of dynamic functions such as stress relaxation, self-healing, reprocessing, and fusion of heterogeneous networks, were achieved. These findings provide new design guidelines for the development of recyclable and long-lived polymeric materials with reorganizable structures and tunable properties.